Process of making active material for storage-battery electrodes.



J. W. AYLSWORTH.

PROCESS 0F MAKING ACTIVE MATERIAL FOR STORAGE BATTERY ELBGTRODBS.

APPLICATION FILED PEB.6,1908.

938,45 1 Patented Oct. 26, 1909.

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UNITED sTATEs PATENT oE-EioE.

JONAS W. AYLSWORTH, OF EAST ORANGE, NEW JERSEY, ASSIGNOR TO EDISON STORAGE BATTERY COMPANY, OF WEST ORANGE, NEW JERSEY, A' CORPORATION OF NEW JERSEY.

PROCESS OF MAKING ACTIVE MATERIAL FOR STORAGE-BATTERY ELECTRODES.

Specification of Letters Patent. i .Patented Oct. '26, 1909.

Original application filed April 28, 1905, Serial No. 257,875. Divided and this application led February G,

1908. Serial No. 414,558. l

To all whom 'it may concern:

Be it known that I, J oNAs W. AYLsWoRTH, a citizen of the United States, and a resident of East Orange, in the county of Essex and State of New Jersey, have invented certain new and useful Improvements in Processes of Making Active Material for Storage- Battery'Electrodes, of Which the following is a description. I

This application is a division of my application Serial No. 257,875, filed April 28th, 1905 Which on March 3, 1908, became Patent No. 880,957.

My invention relates to a process for making active material for use in ,storage battery electrodes of the type employing an alkaline electrolyte with insoluble active materials, and-particularly for use in the positive or depolarizing electrodes in Which the active mass consists of nickel hydroxid, as in the Well-known Edison battery.V

My invention may be used either in direct connection With the manufacture of the improved electrodes, or as a separate operation for use in the make-up of electrodes of other types, as for instance, the Well-known Edison electrode, wherein the active mass isv admiXed with Hake-like conducting material (such as flakes of metallic cobalt or of cobaltnickel alloy) and maintained under suitable pressure Within perforated containing pockets.

The object of my invention is to provide a simple and effective process for making storage battery electrodes and active material therefor of high electrolytic activity and at low cost.

The inventiondepends upon the fact that hydratedl peroXid of nickel--Ni(OH)3- can be formed in and plated out of `a cyanid solution electrolytically. Such a hydrated peroxid is electrically conducting and unlike metals in a plating-bath it deposits on the anode instead of on the cathode. Consequently, no deposit takes place on the cathode, which Willl not be affected bythe hydrogen developed thereon, except to the extent that it will be very perfectly cleaned by the reducing and mechanical scouring action ofthe hydrogen gas.

The anode isl .alkaline solution used, any oxygendeveloped instance, the ordinary perforated pockets of the Edison battery.

In order that the invention may be-better understood, attention is directed to the accompanyingdrawings forming part ofthis specification, and in Which- Figure l is a diagrammatic view of a suitable apparatus used in connection With the manufacture of hydrated peroxid of nickel electrolytically, when the latter is not to be employed directly, but is to be removed from the anode on Which it is deposited and separately used in connection With the electrode support. Fig. 2 is a view in vertical cross section of one form of anode so arranged that the deposit may be made thereon. Fig.

'3 is a similar sectional view, showing the parts of the anode shown in Fig. 2 reversed to form the completed battery element, and Fig. 4; is an enlarged sectional detail of the battery element shown in Fig. 3.

In these views corresponding parts are represented by the same numerals of reference.

Referring first to Fig. l, I show a plating tank l, made' of any suitable material, With the cathode 2 therein, formed of a plate of insoluble' material not aifected by electrolysis Whenused as a cathode in a cyanid solution, such as graphite or iron, or nickel or cobalt, or nickel-cobalt alloy. The anode 3 is in the 4form of a long endless strip, such as'nickel or cobalt, or nickel-cobalt alloy passing over rollers 4 and driven in any suitable Way, as for instance, by an electric also unaffected yfor the reason thatin the motor 5. Bearing on this anode strip are two brush wheels or scrapersf, for removing material deposited on the anode, as will be understood. Current is supplied from a plating dynamo 7, the vconnections being obvious. 1With such yan apparatus (which of course is merely illustrative) I form the ac- -tive material electrolytically in any suitable way, examples of which are the following: (l) Cyanid of potassium (KCy.) yis added to a solution of a soluble nickel salt, such as the sulfate (NiSOQ or the chlorid (NiClz), until the precipitate which at first orms, is nearly all redissolved. Io this solution, I then add preferably an equal volume of 2 0 per cent. solution of potassium hydroxid, (KOH) both solutions being preferably hot. Good vresults can be secured whena much smaller volume of the alkaline solution is employed, but preferably a great excess of alkali is used,in order to reduce the likelihood of the anode being attacked electrolytically. When .such a solution is employed, (for instance in the tank 1) the current results in the electrolytic deposition of the hydrate peroxid of nickel on the anode 3, which deposit'may be removed by the revolving brushesf, as will be `understood. With this solution, the plating is preferably carried on at a high rate (f\or in stance .5 ampere per square inch, or even ymore) since in this way the deposit is detached more easily than' when.the deposit l takes place slowly.

(2) A' solution of cyanid of potassium (KCy) is first saturated with nickel 'cyanid (NiCy2) after which an equal volume of 20. per cent. potassium hydroxid (KOH) is added. 'Ilo `the clear solution thus obtained, I then add a quantity of cyanid of nickel, which remains as a precipitate in the solution? and the amount of which may be varied within wide limits. Withsuch a solution, the plating operation is preferably carried on as rapidly as in the first example. As the nickel eroxid. is plated out of the solution, it wil be automatically regenerated from the cyanid of nickel precipitated therein. As this precipitate lthus becomes dissipated, .additional quantities of nickel cyanid may be added to the solution from time to time. nid for this purpose, nickelous hydrate Ni (OH) may be used, although not so effectively.

A solution made in accordance with the second example gives the best results, particularl when the process isem loyed for depositingthe active material irectly on the electrode lsup ort, as I shall explain,

Instead of using nickel cyawhere the process is employed for manufacturing the active material independently of the electrode support and where very thick layers of the active material are not necesv soda, with an excess of sodium hydrate.l

Double cyanids of lithium, calcium and barium with nickel may also be used, as well as combinations of such cyanids.

It will be evident that instead of depositing the active material on an anode from which the active material is removed either continuously, or from time to time, the anode itself may ccnstitute the electrode support, whereby the electrolytic deposit of the active material on'that support will be carried out as one of the steps of a process for making electrodes.

In Figs. 2, 3 and 4 I have shown two plates 8, having minute openings punched therein, so as to form projecting burs, (F ig. 3) and these plates are placed together with the burs extending outwardly and temporarily held by clips or bands 9 (Fig. 2) They are now used as anodes in a suitable plating bath, preferably in connection with the solution made according tothe second example labove described, and the'nickel hydroxid is it unnecessary to employ separate flakes of conducting material, as is desirable where comparatively thick masses of active material arevto be used.

" Of course, many other forms of plates 0rother electrode supports maybe employed than those described, the essential idea be; ing to provide an arrangement by which the active material may adhere tenaciously to the anode support on which it is deposited. I find, however, that where the deposit takes place slowly from solution the latter should be kept" at about 8O degrees centigrade, and if not too thick it will adhere satisfactorily to a plain plate, neither corrugated nor perforated. It will be understood that in any event the anode or electrode support on which the active material is depossince the deposite peroxid is very ure and ited, should be made of some material not afthere are no acid radicals in the so ution to fected by electrolysis in alkaline solution', interfere with'the deposit4 With the soluand capable of good contact with the active tion first described, such a result might take l material, preferably sheets of metallic cobalt place, but that solution is entirely usefull o" cobalt-nickel alloy, ord sheet steel plated with cobalt or cobalt-nickel alloy, as described in the patent to Thomas A. Edison, No. 882,144, granted March 17 1908.

I claim- 1. The process of making active material for storage batteries, Which consists in electrolytically forming the active material in and depositing the same out of a cyanid so# lution thereof, substantially as set forth.

2. rlhe process of making active material for storage batteries, which consists in depositing nickel peroxid electrolytically out of a cyanid solution thereof, substantially as set forth.

3. The process of making active material for storage batteries, Which consists in depositing nickel peroXid electrolytically out of a cyanid solution thereof, in which exists a mass lof a nickel salt to regenerate the solution,` substantially as set forth.

4. The process of making active materiall for storage batteries, which consists in depositing nickel peroXid electrolytically out of a cyanid solution thereof, and in Which exists a mass of nickel cyanid to regenerate the solution, substantially as set forth.

5. The process of making active material for storage batteries, Which consists in plating the active material out of a cyanid solution of the same on a moving anode and continuously removing the deposit therefrom, substantially as set forth.

6. The process of making active material for storage batteries, Which consists in continuously platino` nickel peroXid out of a cyanid solution of the same upon a moving anode and in continuously removing the deposit therefrom, substantially as set forth.

This speciiication signed and witnessed this 1st day of Feb. 1908. 1

JONAS W. AYLSWORTH.

Witnesses:

`M. JOHNSON,

FRANK L. DYER. 

